Process for conversion of hydrocarbon oils and similar substances



Feb. 19 1924.

V. L.. EMERSON PROCESS FOR CONVERSION OF HYDROOARBON OILS AND SIMILAR SUBSTANCES Filed Nov. 5, 1919 "LA" Q r l v{ 4 J m .J Ur; R h

BY v ,ATTORNEY Patented Feb. 19, 1924.

UNTED STATES Mateu VICTOR LEE EMERSON, OE PHILADELPHIA, PENNSYLVANIA.

PROCESS FOR CONVERSION OF HYDROCARBON'OILS AND SIMILAR SUBSTANCES.

Application med November' 3, 1919. 'serial No. 335,563.

To all whom t may concern vBe it lrnowrrthatv I, Vieron LEnEMnRsoN, a citizen of the United States, residing at Philadelphia, Pennsylvania, have invented certain new and useful Improvements in Processes for Conversion of Hydrocarbon Oils and Similar Substances, of which the following is a specification.

'Vhile lthis invention relates broadly to the distillation and conversion ofcomplex chemical combinations into new atomic groups, it relates more specifically to a process for the. conversion of heavy hydrocarbons into a lighter product and to eliminate largely the sulphur and water and other similar foreign compounds to prevent them from forming objectionable combinations 1n the still, such as carbon bisulphide, and to prevent the elements of oxygen and hydrogen contained in the water from formmg explosive compounds 'by uniting with the hot carbonaceous vapors in the still. yOll stills have usually been fed directly with the oil before previously treating the same with the result that hard carbon formations are formed in the stills, which it is difficult to remove. often resulting in the still burning out. Violent explosions have also taken place when there was apparently but little pressure on the stills. These are apparently due to the result of a small quantity of water or moisture being pumped into the stills while they were at high temperature. Also sulphur accompanies the oil in many cases. The oxygen of thewater, combining with the carbonaceous gases, forms chemical combinations in which combustion takes place rapidly supported by the hydrogen contained in the water and the sulphurous gases present. and violent explosions follow.

lith the present method these dangers are entirely avoided, as they contained water and sulphur compounds are removed prior to.

the introduction of thefheavy oil ilnto the r still.

lt is an object of the present invention to provide vfor the removal of foreign compounds from the heavy oil prior to the admission of the same into the still.

It is a further object of the present invention to utilize the heat in the gaseous products coming from the still to pre-heat the bil i oils before they are pumped into the still to evaporate any water held in suspension and to remove any sulphurous compounds that might enter into combination with either the oil or water or the gaseous products therefrom. At the same time a-portion of the heavier products coming' over in gaseous form from the still are condensed by contact with the incoming supply of fresh oil which vis at a lower temperature and conversely such readily volatilizablematerial in the incoming oils is transformed into gaseous form by the heat'xtransmitted to the same from the gaseous products which come in contact with the fresh oils.

It is likewise'an object of this invention to subject the fresh supply of incoming oil to the action of the jets and the heat of the.

gaseous products from the still and to combine the same with such products from thestill as are condensed on contact with the fresh supply of oil. 'The preheated and pretreated fresh oil and condensates are injected into the material contained inthe still and are subjected to acracking reaction by rea' into which they are injected isat a com-' paratively higher boiling point and a comparatively higher temperature .than the material injected, this being due to the fact that the material in the still has been robbed of the oil of lower boiling points by distillation.

In carrying out my process the hydrocar bons having a relatively low boiling point are subjected to the residual hydrocarbons undergoing treatment under relatively higlf` pressure and temperature and which have a relatively high boiling point. of the relatively `loWboiling hydrocarbons to the relatively high boiling material in the still not only utilizes the temperature and heat of the high 'boiling h drocarbons to cause a cracking reaction o the lower boiling hydrocarbons, but the low boilin hydrocarbons, when intermixed with kthe high boiling hydrocarbons, act to maintain the entire mixture in such a state as to avoidV the formation of hard carbon and free gas The supply by excessive cracking due to the extreme temperatures accompanying a reduction of the distillate to a very high boiling point with its attendant high temperature which is present to a large extent in the well known processes. j

It is a still further object to utilize the pressure and velocity of the gaseous products as they come from the still to produce molecular dissociation by impact either of the gaseous products themselves or in combination with the heavy oil, the molecular dissociation lby impact producing a condition inducive to the formation of new latomic groups and aid the production of a product of lighter specific gravity. j

1t is a still further object to utilize the kinetic energy contained in the aseous products as they come from the sti l to produce an ionizing or similar effect that is inducive to the formation of new atomic groups.

Other objects and advantages of the invention will appear hereinafter. In my Patents Nos. 1,367,807, Feb. 8, 1921; 1,346,797, July 13, 1920; 1,346,798, July 13, 1920; 1,414,400, May 2, 1922; granted upon copending applications and copending application. Serial No; 380,171, filed May 10,

'1920, all of which are continuations in part of this application, l have claimed certain processes and apparatus which are disclosed in this application but not claimed herein.

1n order to render my present invention clear, reference is had to the accompanying drawings in which- The figure is a vertical section of one form of my device as adapted for carrying out the conversion of petroleum.

In the apparatus disclosed in the drawings for carrying out the process of conversion, a receptacle 1 of any desired shape or size is provided to which the heavy hydrocarbon 2 is fed through a suitable feed pipe 3, which is controlled by a valve 4. This valve may be either manually or automatically controlled to maintain a certain predetermined quantity of heavy Huid in the apparatus, the valve 4 as herein shown being controlled by a float 5 which is adjustable by the thumb screw 6 seated in the top wall of the receptacle. The revoluble member of the valve 4 is connected to the float 5 by means of a bar 5. The Hoat in its vertical movement controls the degree of oscillation of the' valve 4 and brings the opening in the periphery 4 of the latter into or out of register with the feed pipe 3 and the receptacle 1 for the purpose tobe hereinafter described. The bottom of the receptacle 1 is preferably tapered toward a central outlet 7 controlled by a gate valve or other closure means 8 through which the carbonaceous and other solid material may be drawn oli' from time to time. A suitable pedestal 9 is provided for supporting the receptacle 1 at a convenient height to permitnthe valve 8 to be manipulated.` 1n the lower portion of the wall of the receptacle an outlet pipe 10 is provided, through which outlet the contents of the receptacle, after treatment therein, may be pumped or forced. to the still. It will thus be evident that the above apparatus forms an intermediary. between the source of supply and the still. Within the apparatus the supply is purified, preheated and predistilled to a certain extent. It also follows that the fresh material will serve to condense such portions of the gaseous products passing through said material as are condensable at the temperature at which the material is maintained. These condensates along with the predistilled oil are now carried to the still through the pipe 10 and are injected into the material contained in the still which has a relatively higher boiling point and higher temperature.

The top wall of the receptacle 1 has a central opening with a downwardly depending member 11, which member terminates in a vertical pipe 12, the lower end of which carries a flaring or bell-shaped member 13. This bell-shaped member extends to points adjacent the wall of the receptacle 1 and is there perforated with a series of holes 14. Surrounding the member 11 and concentric therewith is a tubular baiile member 25 for the purpose of promoting circulation within the receptacle.

Diametrically disposed in the top wall of the receptacle 1 are mounted vertical pipes 15 termlnatin'g at their lower portion and below the flanged member 13 in elbows 16, the inner ends of the elbows being open and providing free entry for the fluid contained in the receptacle into the pipe 15. The upper ends of the pipes 15 are connected through regulating valves 17 with the chambered cross pipes 18. The pipes 18 terminate radially of the receptacle 1 in jet nozzles 19 having a common axis through the diameter of the receptacle 1. A reaction chamber 20, whichis mounted upon the top wall of the receptacle 1., and in continuation of the pipe 11, is adapted to surround the jets 19.

Entrant .jets 21k form part of the cross member 18 and terminate above the axis of the pipes 15. `The entrant jets are fed from a manifold 22 which is adapted for connection to the still by ymeans of pipe 24 and a regulating valve 23 to control the supply of gaseous products` therefrom. `Whle only two jets or nozzles are shown in the present modification, it is of course to be understood that any number of jets, together with their accompanying pipes 15, may be employed, or

' a single jet may play on a baffle.

products to a condenser or other suitable apparatus for receiving and separatingV the products of the process according to their volatility or power of absorption.

In carrying out the present process, valve 23 is opened permitting the gaseous products under relatively high pressure from the still or boilerl to pass through the manifold 22 into the jets or nozzles 21. While my process is capable of being carried out through a wide range of temperatures and pressurps and the details of the apparatus are capable oi variation within the scope of my invention, which is not limited to the particular temperatures, pressures or details mentioned, the following is given as an example of the execution of my process in a particular instance. I find that satisfactory resultswill be .obtained by the use of apressurel in the still of one hundred pounds per square inch with an accompanying temperature of seven hundred to eight hundred degrecs F. In order to impart the' proper kinetic energyl to the gaseous products at such a temperature and pressure satisfactory results may be obtained by the use of a jet apparatus following a design based upon the standard practice in connection with steam'- injectors for the feed water of boilers. By regulating the oil supplied to the jets the liquid in the base 1 canbe maintained at a point which will condense those portions of the products of impact which it is desirable to subject to further dissociation and allow the gaseous products to pass 'od which compose the final product.v The fiuid or vapors from the still pass through these jets which impinge upon each other in the reaction chamber 20. The jets' are so designed as to give the gases issuing therefrom a very high velocity and the kinetic energy imparted to the gaseous products, is expended at .the point of impact of the jets.

It is of course unnecessary to go into an extended discussion of the reactions that take place at the point of impact ofthe jets. While not limiting myself to any one theory or hypothesis, it would appear that the high velocity of the gaseousproducts gives rise to a molecular attrition of extreme violence at the point of impact and a large amount of heat is liberated at this point, the developl ment and liberation of heat at the point of impact of the gaseous streams acting to dissociate the molecules. The preheating of the hydrocarbon mass causes the hydrocarbons to approach the point of impact under relatively high temperature and consequent readiness to split up or, as it is technically known, be cracked by the action of impact. This dissociation is further aided by the shock of impact and the attendant phenomena of attrition which not only givesrise to heat by friction, but promotes the reduction of the mass into its constltuent molecules. The dissociation of the molecules with Vthe attendant atomic rearrangements gives rise to new and simpler atomic groups. In obtaining this dissociation by impact and its attendant phenomena, there is an absence of the surrounding pressure which would otherwise be essential were it to be carried out in a confined chamber under simpler hydrocarbons resulting'from this reaction.

The gaseous products from this step now pass down the pipe 11v and bubble up through the body of liquid 2 in the receptacle 1. In this way the heat brought over by the stream of volatile material from the still and the heat caused by the impact of the jets, serves to heat the body of liquid asa preliminary step 4to its treatment in the still. By this means the temperature of the receptacle and its contents `is kept well above the boiling point of Water and the water contained in the heavy oil is thereby entrained as vapor by the gaseous products .and carried out through the vapor dome 26, together with the sulphur vapors' and sulphurous compounds. By this action the heavy oil is dehydrated and desulphurized prior to its treatment in the still, and the lighter hydrocarbons already existing in the heavy oil are ractionally removed before they enter the still. It may also be possible that some additional action may take place between the freely ionized gaseous products from the jets and the heavy material in the receptacle. j

The use of the baffle member 25 serves to set up lconvection currents which materially aid in the heating loi the material and the separation of solid material from the oil before ltreatment in thestill. The upwardly moving material carries the 'gaseous products .in bubbles which, re-

under certain circumstances to inject intoy o periodi- .125

the reaction chamberV and in the field ot the impinging jetsa certain proportion. of the crude oil. By suitable manipulation of the valves 17 the nozzles-19 and 21 constitute injectors which serve to lift the liquid through the pipes 15, mix; it With the incoming jets of hotgaseous products from the still, and project the mixture at high velocity into the reaction chamber 20 Where it is subjected to treatment by heat and impact. In actual operation it is desirable to operate the valve 17 so as to regulate the flow of oil to the jets in such a manner that in the preliminary steps to operation a lsuiiicient flow of oil may be passed through the jets to quickly heat up the oil to the desired point. The flow of oil is then diminished to such a point that the gaseous products may impart a high' velocity to the same in a very finely divided state. Thereafter they are subjected to impact with its consequent reaction. In this manner the breaking .down of the higherihydrocarbons from the still lis promoted, and the Water vapor present in the oil may enterl into the reaction ytaking place at the jets, a hydrogenating effect taking place". added to the heavy oil in the receptacle. or directly to the jets in order to increase the hydrogenating e'ect. Hydrogen gas could also be admitted in the same manner and for the same purpose. By passing the oil directly through the jets a large proportion of the heavy oil undergoes treatment and lighter hydrocarbons are formed therefrom Without the necessity of subjecting the entire body oi heavy oil to treatment in the still. 'In connection with Figure 1 I have shown a conventional form. of still and indicated the connections between it andthe apparatus therein diss closed. As will be seen, the preheated and pretreated fluid in receptacle 1 is supplied to the still by a pump to which the pipe 1() is connected. The heated gaseous products under pressure from the still are indicated as being supplied to the pipe 24.

In the cycle of operations'followed in carrying out my method the still supplies hydrocarbon gaseous products under .pres-k sure and heat to the jets 19 Where the' gaseous products are treated by impact. The heavy hydrocarbon oils are also treated by impact repeatedly since they pass up through the pipe 15- into the iniluence of the jets. Such portion of the products of this treatment of heavy hydrocarbon oil by impact and the products otthetreatnient of the gaseous products from the still by impact as are not removed in the gaseous state through the pipe 27 are suplied t0 the still.,- thus completing the cyc e of operations.

The products of distillation which come If desired, Water could bey Lesagoaa between the ilnpinging jets, but it should be understood that this term not only covers a mechanical attrition but a molecular and atomic attrition as Well in the present instance.

It will be apparent that the gaseous products and liquid hydrocarbons are rapidly subjected to temperature changes.

'Ihe gaseousproducts on reaching the jets have been cooled by expansion, thereafter they are heated by impact and are again cooled by being brought in contact With the liquids in the receptacle which are maintained at a lower temperature than the gases. 'Ihe liquids in the receptacle are raised in temperature by intermixture with the gaseous products from the still and undergo the temperature changes along with these gaseous products. -This constant rapid change of temperature promotes dissociation of the hydrocarbon molecules by subjecting them to repeated and sudden changes in stress due to the temperature changes which tend to overcome their chemical inertia.

Vhile the particular embodiment of my invention has been described with reference to the treatment of petroleum for the production of lighter hydrocarbons, it is of course to be understood that the same process is equally applicable to chemical compounds other than hydrocarbons.

It `is also to be understood that other conditions and reactions than those dcscrlbed may be present in the process and Within the scope of the invention as defined" in the appended claims.

What I claim is:- y

1. The process of conversion of hydrocarbon oils which consists in impartingsufficient kinetic energy to a mass of the same to cause dissociation on impact, subjecting said energized mass to impact, repeatedly subjecting the resultant products to impact together With a portion of fresh hydrocarbon oil, subjecting the products of impact thus formed to intimate contact with the hydrocarbon oil and drawing oii` the gaseous products.

2. The process of conversion of hydrocarbon oils which consists in imparting sufiicient kinetic energy to a mass of the same to cause dissociation on impact, subjecting said energized mass toimpact by the mutual impingement of jets of the same, subjecting the resultant products to impact, imparting ginetic energy to a separate mass of hydrocarbon oil by mixing the A same with said irst mentioned energized mass, subjecting the mixture to impact, subjecting the products of impact thus formed to intimate Contact with a fresh mass of hydrocarbon oil and separating out the resultant products.

In testimony whereof I have hereunto set my hand.

VICTOR LEE EMERSON. 

